CN102144017A - Liquid crystal composition and liquid crystal display element - Google Patents

Liquid crystal composition and liquid crystal display element Download PDF

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CN102144017A
CN102144017A CN200980134649XA CN200980134649A CN102144017A CN 102144017 A CN102144017 A CN 102144017A CN 200980134649X A CN200980134649X A CN 200980134649XA CN 200980134649 A CN200980134649 A CN 200980134649A CN 102144017 A CN102144017 A CN 102144017A
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liquid
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斎藤将之
服部宪和
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JNC Corp
JNC Petrochemical Corp
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Chisso Petrochemical Corp
Chisso Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
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    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition

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Abstract

Disclosed is a liquid crystal composition which satisfies at least one of such characteristics as high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, adequate optical anisotropy, large negative dielectric anisotropy, high resistivity, high stability against ultraviolet light and high stability against heat, or has an adequate balance between at least two of the above-mentioned characteristics. Also disclosed is an AM element having a short response time, high voltage holding ratio, high contrast ratio, long life and the like. The liquid crystal composition contains a specific compound having tetrahydropyran-2,5-diyl as a first component, and a specific compound having a large negative dielectric anisotropy as a second component, and has a negative dielectric anisotropy.

Description

Liquid-crystal composition and liquid crystal display device
Technical field
The present invention mainly relates to a kind of active-matrix (active matrix, AM) liquid-crystal composition of element etc. and contain AM element of this constituent etc. of being suitable for.The present invention particularly is negative liquid-crystal composition relevant for a kind of dielectric constant anisotropy (dielectric anisotropy), and relevant for a kind of transverse electric field switching (in-plane switching that contains this constituent, IPS) pattern, vertical orientation (vertical alignment, VA) pattern or polymkeric substance continue orientation (polymer sustained alignment, PSA) element of pattern etc.
Background technology
In liquid crystal display device, be categorized as phase change (phase change based on the operating mode of liquid crystal, PC), twisted nematic (twisted nematic, TN), STN Super TN (super twisted nematic, STN), electrically conerolled birefringence (electrically controlled birefringence, ECB), optical compensation curved (optically compensated bend, OCB), transverse electric field switches (in-plane switching, IPS), vertical orientation (vertical alignment, VA) and polymkeric substance continue orientation (polymer sustained alignment, PSA) pattern etc.Based on the type of drive of element be categorized as passive-matrix (passive matrix, PM) with active-matrix (active matrix, AM).PM is classified as static state (static) and multiplex (MUX) (multiplex) etc., AM be classified as membrane transistor (thin film transistor, TFT), metal-insulator-metal type (metal insulator metal, MIM) etc.TFT is categorized as non-crystalline silicon (amorphous silicon) and polysilicon (polycrystal silicon).The latter is categorized as high temperature modification and low temperature modification according to process quilt.Utilize the reflection-type of natural light based on being categorized as of light source, utilize the penetrating type of (backlight) backlight, and the semi penetration type that utilizes natural light and both sides backlight.
Those elements contain the liquid-crystal composition with appropriate characteristics.This liquid-crystal composition has nematic phase.The general characteristic that promotes constituent in order to obtain to have the AM element of good general characteristic.Both relations of general characteristic are summarized in the following table 1.Further specify the general characteristic of constituent based on commercially available AM element.The spendable temperature range of nematic temperature range and element is relevant.Nematic ceiling temperature preferably is more than or equal to 70 ℃, and nematic lower limit temperature preferably is smaller or equal to-10 ℃.The viscosity of constituent is relevant with the time of response of element.In order in element, to show dynamic image, be preferably the short time of response.Therefore, it is little to be preferably the viscosity of constituent.The viscosity that is more preferably under the low temperature is little.
The general characteristic of table 1. constituent and AM element
1) can shorten the time that constituent injects liquid crystal cells
The optical anisotropy of constituent is relevant with the contrast gradient of element.With the optical anisotropy (Δ n) of constituent and cell gap (cell gap) product (the Δ n * d) be designed so that contrast gradient becomes maximum (d) of element.Suitable product value depends on the kind of pattern.Being the scope of 0.30 μ m to 0.40 μ m in the element of VA pattern, is the scope of 0.20 μ m to 0.30 μ m in the element of IPS pattern.When this situation, in the less element of cell gap, be preferably constituent and have big optical anisotropy.The dielectric constant anisotropy that the absolute value of constituent is bigger helps to reach the lower critical voltage of element, less consumption electric power and big contrast gradient.Therefore, it is bigger to be preferably the absolute value of dielectric constant anisotropy.The bigger resistivity of constituent helps to reach the big voltage retention of element and big contrast gradient.Therefore, be preferably constituent in the early stage the stage not only at room temperature have bigger resistivity, and at high temperature also have bigger resistivity.Be preferably constituent and after long-time the use, not only at room temperature have bigger resistivity, and at high temperature also have bigger resistivity.Constituent is relevant to the life-span of ultraviolet and hot stability and liquid crystal display device.Those are stable when higher, and the life-span of this element is long.This specific character helps liquid crystal projector (liquid crystal projector), employed AM element in the LCD TV (liquid crystal television) etc.
In having the AM element of TN pattern, use constituent with positive dielectric constant anisotropy.On the other hand, in having the AM element of VA pattern, use constituent with negative dielectric constant anisotropy.In having the AM element of IPS pattern, use the constituent of dielectric constant anisotropy with plus or minus.In having the AM element of PSA pattern, use the constituent of dielectric constant anisotropy with plus or minus.Example with liquid-crystal composition of negative dielectric constant anisotropy is disclosed in following patent documentation 1 and 2.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent spy opens the 2001-262145 communique
[patent documentation 2] Japanese Patent spy opens the 2001-115161 communique
Ideal AM element has with inferior characteristic: spendable temperature range is wide, and the time of response is short, and contrast gradient is big, and critical voltage is low, and voltage retention is big, and the life-span is long.Comparatively ideal is to be shorter than 1 millisecond the time of response.Therefore, the ideal behavior of constituent is: nematic ceiling temperature height, and nematic lower limit temperature is low, viscosity is little, and optical anisotropy is suitable, and the dielectric constant anisotropy of plus or minus is big, resistivity is big, and is high to ultraviolet stability, stable high to heat.
Summary of the invention
An object of the present invention is a kind of liquid-crystal composition that in following characteristic, fully possesses at least a characteristic: nematic ceiling temperature height, nematic lower limit temperature is low, viscosity is little, optical anisotropy is suitable, the negative value of dielectric constant anisotropy is big, resistivity is big, and is high to ultraviolet stability, stable high to heat.Another object of the present invention is a kind of suitable equilibrated liquid-crystal composition that has at least two specific characters.Another purpose of the present invention is a kind of liquid crystal display device that contains this kind constituent.Another purpose of the present invention is a kind ofly to have little optical anisotropy or big optical anisotropy is suitable optical anisotropy, big negative permittivity anisotropy, constituent to ultraviolet high stability etc., and a kind ofly have the short time of response, big voltage retention, big contrast gradient, the AM element of long lifetime etc.
A kind of liquid-crystal composition and the liquid crystal display device that contains this liquid-crystal composition, this liquid-crystal composition contains being selected from at least a compound in the group of the represented compound of formula (1) as first composition, and as being selected from at least a compound in the group of the represented compound of formula (2) of second composition, and it has negative dielectric constant anisotropy.
Figure BPA00001328390700031
Herein, R 1And R 2The thiazolinyl (alkenyl) of independent alkoxyl group (alkoxy), carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl (alkyl) of carbon number 1 to 12, carbon number 1 to 12; Ring A independently is a tetrahydropyrans-2,5-two bases (tetrahydropyran-2,5-diyl), 1, the 4-cyclohexylidene (1,4-cyclohexylene) or 1, the 4-phenylene (1,4-phenylene), and at least one to encircle A be tetrahydropyrans-2,5-two bases; Ring B and ring C independently are 1,4-cyclohexylidene or 1,4-phenylene; Z 1And Z 2Independent is singly-bound, ethylidene (ethylene), inferior methoxyl group (methyleneoxy) or carbonyl oxygen base (carbonyloxy); M is 1,2 or 3; P and q independently are 0,1,2 or 3, and p and q's and more than or equal to 3.
[effect of invention]
Advantage of the present invention is a kind of liquid-crystal composition that fully possesses at least a characteristic in following characteristic: nematic ceiling temperature height, nematic lower limit temperature is low, viscosity is little, optical anisotropy is suitable, the negative value of dielectric constant anisotropy is big, resistivity is big,, stable high to heat high to ultraviolet stability.An aspect of of the present present invention is a kind of suitable equilibrated liquid-crystal composition that has at least two specific characters.Another aspect of the present invention is a kind of liquid crystal display device that contains this kind constituent.Another aspect of the present invention be a kind ofly have suitable optical anisotropy, big negative permittivity anisotropy, to the constituent of ultraviolet high stability etc., and a kind of AM element with short time of response, big voltage retention, big contrast gradient, long lifetime etc.
Description of drawings
Do not have
Embodiment
The using method of the term in this specification sheets is as follows.Sometimes abbreviate liquid-crystal composition of the present invention or liquid crystal display device of the present invention as " constituent " or " element " respectively.Liquid crystal display device is the general name of display panels and liquid-crystal display module." liquid crystal compounds " be meant have nematic phase, compound that stratose equates mesomorphic phase or do not have mesomorphic phase but as the useful compound of the composition of constituent.This useful compound for example has as 1, and 4-cyclohexylidene or 1, the six membered ring of 4-phenylene, its molecular structure are bar-shaped (rod like).Sometimes optically active compound or polymerisable compound are made an addition in the constituent.Even if those compounds are liquid crystal compounds, also be classified as additive herein.Sometimes will be selected from at least a compound in the group of the represented compound of formula (1) and abbreviate " compound (1) " as." compound (1) " is meant with represented a kind of compound of formula (1) or two or more compound.The compound represented with other formulas is also identical." arbitrarily " refer to that not only the position is arbitrarily, also refer to that number is arbitrarily, but do not comprise that number is 0 situation.
Sometimes abbreviate nematic ceiling temperature as " ceiling temperature ".Sometimes abbreviate nematic lower limit temperature as " lower limit temperature "." resistivity is big " be meant constituent in the early stage the stage not only at room temperature and at high temperature also have bigger resistivity, and after long-time the use, not only at room temperature and at high temperature also have bigger resistivity." voltage retention is big " be finger element in the early stage the stage not only at room temperature and at high temperature also have big voltage retention, and after long-time the use, not only at room temperature and at high temperature also have big voltage retention.When characteristics such as explanation optical anisotropy, use by the value of being put down in writing among the embodiment that measuring method obtained.First composition is a kind of compound or two or more compound." first components in proportions " is meant the weight percent (wt%) of first composition with respect to the gross weight of liquid-crystal composition.Second components in proportions etc. are also identical.The ratio of institute's blended additive is meant weight percent (wt%) or the weight part per million (ppm) of described additive with respect to the gross weight of liquid-crystal composition in the constituent.
In the chemical formula of component cpd, with R 1Symbol be used for a plurality of compounds.In any two compounds in those compounds, R 1Implication can be identical, also can be different.The R that for example has compound (1) 1Be ethyl, the R of compound (2) 1Example for ethyl.The R that also has compound (1) 1Be ethyl, the R of compound (2) 1Example for propyl group.This rule also is applicable to R 2, Z 1Deng.
The present invention is a following item etc.
1. liquid-crystal composition, it contains as being selected from at least a compound in the group of the represented compound of formula (1) and as being selected from at least a compound in the group of the represented compound of formula (2) of second composition of first composition, and described liquid-crystal composition has negative dielectric constant anisotropy.
Figure BPA00001328390700051
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring A independently is a tetrahydropyrans-2,5-two bases, 1,4-cyclohexylidene or 1, the 4-phenylene, and at least one to encircle A be tetrahydropyrans-2,5-two bases; Ring B and ring C independently are 1,4-cyclohexylidene or 1,4-phenylene; Z 1And Z 2Independent is singly-bound, ethylidene, inferior methoxyl group or carbonyl oxygen base; M is 1,2 or 3; P and q independently are 0,1,2 or 3, and p and q's and more than or equal to 3.
2. as the 1st described liquid-crystal composition, wherein first composition is to be selected from at least a compound of formula (1-1) to the group of the represented compound of formula (1-7).
Figure BPA00001328390700052
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12.
3. as the 2nd described liquid-crystal composition, wherein first composition is to be selected from at least a compound of formula (1-1) to the group of the represented compound of formula (1-3).
4. as the 2nd described liquid-crystal composition, wherein first composition is to be selected from at least a compound of formula (1-4) to the group of the represented compound of formula (1-7).
5. as the 2nd described liquid-crystal composition, wherein first composition be selected from formula (1-1) to the group of the represented compound of formula (1-3) at least a compound and with the mixture of at least a compound of formula (1-4) to the group of the represented compound of formula (1-7).
6. each described liquid-crystal composition as in the 1st to the 5th, wherein second composition is to be selected from at least a compound of formula (2-1) to the group of the represented compound of formula (2-4).
Figure BPA00001328390700061
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring B 1, the ring B 2, the ring C 1, and the ring C 2Independently be 1,4-cyclohexylidene or 1,4-phenylene; Z 1And Z 2Independent is singly-bound, ethylidene, inferior methoxyl group or carbonyl oxygen base; Z 4Be ethylidene, inferior methoxyl group or carbonyl oxygen base.
7. as the 6th described liquid-crystal composition, wherein second composition is at least a compound that is selected from in the group of the represented compound of formula (2-3).
8. as the 6th described liquid-crystal composition, wherein second composition is at least a compound that is selected from in the group of the represented compound of formula (2-4).
As the 1st to the 8th in each described liquid-crystal composition, wherein with respect to the gross weight of liquid-crystal composition, first components in proportions is the scope of 5 weight percent to 70 weight percents, and second components in proportions is the scope of 5 weight percent to 30 weight percents.
As the 1st to the 9th in each described liquid-crystal composition, it contains as ternary being selected from at least a compound in the group of the represented compound of formula (3).
Figure BPA00001328390700071
Herein, R 3And R 4The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring D and ring E independently are 1,4-cyclohexylidene, 1,4-phenylene, 2-fluoro-1, the 4-phenylene (2-fluoro-1,4-phenylene), 3-fluoro-1, the 4-phenylene (3-fluoro-1,4-phenylene) or 2,5-two fluoro-1, and the 4-phenylene (2,5-difluoro-1,4-phenylene); Z 3Independent is singly-bound, ethylidene or carbonyl oxygen base; J is 1,2 or 3.
11. as the 10th described liquid-crystal composition, wherein the 3rd composition is to be selected from at least a compound of formula (3-1) to the group of the represented compound of formula (3-10).
Figure BPA00001328390700081
Herein, R 3And R 4The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12.
12. as the 11st described liquid-crystal composition, wherein the 3rd composition is at least a compound that is selected from in the group of the represented compound of formula (3-1).
13. as the 11st described liquid-crystal composition, wherein the 3rd composition is to be selected from at least a compound in the group of the represented compound of formula (3-1) and with the mixture of at least a compound in the group of the represented compound of formula (3-4).
14. as the 11st described liquid-crystal composition, wherein the 3rd composition is to be selected from at least a compound in the group of the represented compound of formula (3-1) and with the mixture of at least a compound in the group of the represented compound of formula (3-6).
15. as the 11st described liquid-crystal composition, wherein the 3rd composition is to be selected from at least a compound in the group of the represented compound of formula (3-6) and with the mixture of at least a compound in the group of the represented compound of formula (3-10).
16. as the 11st described liquid-crystal composition, wherein the 3rd composition is to be selected from at least a compound in the group of the represented compound of formula (3-1), with at least a compound in the group of the represented compound of formula (3-4) and with the mixture of at least a compound in the group of the represented compound of formula (3-6).
17. as the 10th to the 16th in each described liquid-crystal composition, wherein with respect to the gross weight of liquid-crystal composition, ternary ratio is the scope of 30 weight percent to 70 weight percents.
18. as the 1st to the 17th in each described liquid-crystal composition, it more contains being selected from at least a compound in the group of the represented compound of formula (4) as four-component.
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring F independently is 1,4-cyclohexylidene or 1,4-phenylene; Z 3Independent is singly-bound, ethylidene or carbonyl oxygen base; X 1And X 2Independent is fluorine or chlorine; K is 1,2 or 3.
19. as the 18th described liquid-crystal composition, wherein four-component is for being selected from at least a compound of formula (4-1) to the group of the represented compound of formula (4-7).
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12.
20. as the 19th described liquid-crystal composition, wherein four-component is for to be selected from at least a compound in the group of the represented compound of formula (4-1).
21. as the 19th described liquid-crystal composition, wherein four-component is for being selected from at least a compound in the group of the represented compound of formula (4-1) and with the mixture of at least a compound in the group of the represented compound of formula (4-5).
22. as the 18th to the 21st in each described liquid-crystal composition, wherein with respect to the gross weight of liquid-crystal composition, the ratio of four-component is the scope of 5 weight percent to 55 weight percents.
23. as each described liquid-crystal composition in the 1st to the 22nd, wherein nematic ceiling temperature is more than or equal to 70 ℃, optical anisotropy under wavelength 589nm (25 ℃) is more than or equal to 0.08, and the dielectric constant anisotropy (25 ℃) of frequency when being 1kHz is smaller or equal to-2.
24. a liquid crystal display device, it contains just like each described liquid-crystal composition in the 1st to the 23rd.
25. as the 24th described liquid crystal display device, wherein the operating mode of liquid crystal display device is VA pattern, IPS pattern or PSA pattern, the type of drive of liquid crystal display device is the active-matrix mode.
The present invention also comprises and lising down: 1) more contain the described constituent of optically active compound, 2) more contain the described constituent of additives such as antioxidant, UV light absorber, defoamer.3) contain the AM element of described constituent, 4) contain described constituent, and element with pattern of TN, ECB, OCB, IPS, VA or PSA, 5) contain the penetrating type element of described constituent, 6) with described constituent as the purposes with nematic constituent, 7) by in described constituent, adding optically active compound as the purposes of optical activity constituent.
According to following order constituent of the present invention is described.The first, the formation of the component cpd in the constituent is described.The second, the main characteristic of component cpd and the main effect that this compound brings to constituent are described.The 3rd, illustrate the composition of constituent combination, component cpd ratio preferably with and according to.The 4th, the form preferably of component cpd is described.The 5th, the concrete example of announcement component cpd.The 6th, explanation can be mixed to the additive in the constituent.The 7th, the synthesis method of component cpd is described.The purposes of constituent is described at last.
The first, the formation of the component cpd in the constituent is described.Constituent of the present invention is categorized as constituent A and constituent B.Constituent A also can more contain other liquid crystal compounds, additive, impurity etc." other liquid crystal compounds " is meant and compound (1), compound (2), compound (3) and the different liquid crystal compounds of compound (4).This kind compound is that purpose is mixed in the constituent with further adjustment characteristic.In other liquid crystal compounds, few more good more with regard to cyano compound with regard to the viewpoint of heat or ultraviolet stability.The better ratio of cyano compound is 0 weight percent.Additive is optically active compound, antioxidant, UV light absorber, pigment, defoamer, polymerisable compound, polymerization initiator etc.Impurity is the compound of being sneaked in the step such as synthetic of component cpd etc.Even if this compound is a liquid crystal compounds, also be classified as impurity herein.
Constituent B in fact only is made of the compound that is selected from compound (1), compound (2), compound (3) and the compound (4)." in fact " be meant that constituent also can contain additive and impurity, but do not contain the liquid crystal compounds different with those compounds.Compare with constituent A, the one-tenth mark of constituent B is less.With regard to the viewpoint that reduces cost, constituent B is better than constituent A.For the viewpoint that can further adjust rerum natura by being mixed into other liquid crystal compounds, constituent A is better than constituent B.
The second, the main characteristic of component cpd and the main effect that this compound brings for the constituent characteristic are described.Based on effect of the present invention, the main characteristic of component cpd is summarized in table 2.In the symbol of table 2, L is meant big or high, and M is meant moderate, and S is meant little or low.Symbol L, M, S are based on the classification of the qualitative comparison between the component cpd.
The characteristic of table 2. compound
Compound (1) (2) (3) (4)
Ceiling temperature M～L S～M S～L M～L
Viscosity M～L L S～M M～L
Optical anisotropy M M～L S～L M～L
Dielectric constant anisotropy M～L 1) L 1) 0 S～M 1)
Resistivity L L L L
1) value of dielectric constant anisotropy is a negative value, the size of symbolic representation absolute value
When being mixed to component cpd in the constituent, the main effect that component cpd brings for the constituent characteristic is as follows.Compound (1) is the absolute value that improves dielectric constant anisotropy, reduces lower limit temperature.Compound (2) improves the absolute value of dielectric constant anisotropy.Compound (3) reduces viscosity or improves ceiling temperature.Compound (4) improves optical anisotropy or reduces lower limit temperature.
The 3rd, illustrate the composition in the constituent combination, component cpd ratio preferably with and according to.Being combined as of composition in the constituent: first composition+second composition, first composition+second composition+the 3rd composition, first composition+second composition+four-component and first composition+second composition+the 3rd composition+four-component.Being combined as of composition in the constituent preferably: first composition+second composition+the 3rd composition and first composition+second composition+the 3rd composition+four-component.
In order to improve the absolute value of dielectric constant anisotropy, the ratio preferably of first composition is more than or equal to 5 weight percents, and in order to reduce lower limit temperature, the ratio preferably of first composition is smaller or equal to 70 weight percents.Better ratio is the scope of 5 weight percent to 60 weight percents.Good especially ratio is the scope of 5 weight percent to 50 weight percents.
In order to improve the absolute value of dielectric constant anisotropy, the ratio preferably of second composition is more than or equal to 5 weight percents; In order to reduce viscosity, the ratio preferably of second composition is smaller or equal to 30 weight percents.Better ratio is the scope of 5 weight percent to 25 weight percents.Good especially ratio is the scope of 5 weight percent to 20 weight percents.
In order to reduce viscosity or in order to improve ceiling temperature, ternary ratio preferably is more than or equal to 30 weight percents; In order to improve the absolute value of dielectric constant anisotropy, ternary ratio preferably is smaller or equal to 70 weight percents.In order to reduce viscosity, better ratio is the scope of 35 weight percent to 65 weight percents.In order to reduce viscosity, good especially ratio is the scope of 40 weight percent to 60 weight percents.
In order to improve optical anisotropy, the ratio preferably of four-component is more than or equal to 5 weight percents; In order to reduce lower limit temperature, the ratio preferably of four-component is smaller or equal to 55 weight percents.Better ratio is the scope of 5 weight percent to 50 weight percents.Good especially ratio is the scope of 5 weight percent to 45 weight percents.
The 4th, the form preferably of component cpd is described.R 1, R 2, R 3, and R 4The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12.
In order to improve to ultraviolet ray or hot stability etc., R preferably 1And R 2Be respectively the alkyl of carbon number 1 to 12; Perhaps in order to improve the absolute value of dielectric constant anisotropy, R preferably 1And R 2Be respectively the alkoxyl group of carbon number 1 to 12.In order to improve to ultraviolet ray or hot stability etc., R preferably 3And R 4Be respectively the alkyl of carbon number 1 to 12; Perhaps in order to reduce lower limit temperature, R preferably 3And R 4Be respectively the thiazolinyl of carbon number 2 to 12.
Alkyl is methyl (methyl), ethyl (ethyl), propyl group (propyl), butyl (butyl), amyl group (pentyl), hexyl (hexyl), heptyl (heptyl) or octyl group (octyl) preferably.In order to reduce viscosity, better alkyl is ethyl, propyl group, butyl, amyl group or heptyl.
Alkoxyl group is methoxyl group (methoxy), oxyethyl group (ethoxy), propoxy-(propoxy), butoxy (butoxy), pentyloxy (pentyloxy), hexyloxy (hexyloxy) or oxygen base in heptan (heptyloxy) preferably.In order to reduce viscosity, better alkoxyl group is a methoxy or ethoxy.
Thiazolinyl is vinyl (vinyl), 1-propenyl (propenyl), 2-propenyl, 1-butylene base (butenyl), crotyl, 3-butenyl, 1-pentenyl (pentenyl), pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl (hexenyl), 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl preferably.In order to reduce viscosity, better thiazolinyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl.In those thiazolinyls-steric configuration preferably of CH=CH-depends on the position of two keys.In order to reduce viscosity etc., in thiazolinyl, be preferably trans (trans) as 1-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl.In thiazolinyl, be preferably cis (cis) as crotyl, pentenyl, 2-hexenyl.In those thiazolinyls, the thiazolinyl of straight chain is better than the thiazolinyl of side chain.
The example preferably of the thiazolinyl that replaced by fluorine of hydrogen is 2 arbitrarily, 2-difluoroethylene base (2,2-difluorovinyl), 3,3-two fluoro-2-propenyl (3,3-difluoro-2-propenyl), 4,4-two fluoro-3-butenyls (4,4-difluoro-3-butenyl), 5,5-two fluoro-4-pentenyls (5,5-difluoro-4-pentenyl) and 6,6-two fluoro-5-hexenyls (6,6-difluoro-5-hexenyl).In order to reduce viscosity, better example is 2,2-difluoroethylene base and 4,4-two fluoro-3-butenyls.
Ring A independently is a tetrahydropyrans-2,5-two bases, 1,4-cyclohexylidene or 1, the 4-phenylene, and at least one to encircle A be tetrahydropyrans-2,5-two bases.M be 2 or 3 o'clock any two ring A can be identical, also can be different.In order to improve the absolute value of dielectric constant anisotropy, encircle A preferably and be respectively tetrahydropyrans-2,5-two bases.Tetrahydropyrans-2,5-two bases are
Be preferably
Ring B, ring B 1, the ring B 2, the ring C, the ring C 1, and the ring C 2Independently be 1,4-cyclohexylidene or 1,4-phenylene, p be 2 or 3 o'clock any two ring B can be identical, also can be different, q be 2 or 3 o'clock any two ring C can be identical, also can be different.In order to reduce optical anisotropy, encircle B, ring B preferably 1, the ring B 2, the ring C, the ring C 1, and the ring C 2Be respectively 1, the 4-cyclohexylidene.Ring D and ring E independently are 1,4-cyclohexylidene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-two fluoro-1,4-phenylene, j be 2 or 3 o'clock any two ring D can be identical, also can be different.In order to reduce viscosity, encircle preferably D and the ring E be respectively 1, the 4-cyclohexylidene.Ring F independently is 1,4-cyclohexylidene or 1,4-phenylene, k be 2 or 3 o'clock any two ring F can be identical, also can be different.In order to reduce optical anisotropy, encircle F preferably and be respectively 1, the 4-cyclohexylidene.
Z 1And Z 2Independent is singly-bound, ethylidene, inferior methoxyl group or carbonyl oxygen base, and m and q are 2 or 3 o'clock any two Z 1Can be identical, also can be different, p is 2 or 3 o'clock any two Z 2Can be identical, also can be different.In order to reduce viscosity, Z preferably 1And Z 2Be respectively singly-bound; Perhaps in order to improve the absolute value of dielectric constant anisotropy, Z preferably 1And Z 2Be respectively inferior methoxyl group.Z 3Independent is singly-bound, ethylidene or carbonyl oxygen base, and j and k are 2 or 3 o'clock any two Z 3Can be identical, also can be different.In order to reduce viscosity, Z preferably 3Be respectively singly-bound.Z 4Independent is ethylidene, inferior methoxyl group or carbonyl oxygen base.In order to improve the absolute value of dielectric constant anisotropy, Z preferably 4Be respectively inferior methoxyl group.
X 1And X 2Independent respectively is fluorine or chlorine.In order to reduce viscosity, X preferably 1And X 2Be fluorine.
M is 1,2 or 3.In order to reduce lower limit temperature, m is 1 preferably, and in order to improve ceiling temperature, m is 2 preferably.P and q independently are 0,1,2 or 3, and p and q's and smaller or equal to 3.In order to improve ceiling temperature, p is 2 preferably.In order to reduce lower limit temperature, q is 0 preferably.J is 1,2 or 3.In order to reduce viscosity, j is 1 preferably.K is 1,2 or 3.In order to reduce lower limit temperature, k is 1 preferably.
The 5th, the concrete example of announcement component cpd.In following compound preferably, R 5Alkoxyl group for the straight chain of the alkyl of the straight chain of carbon number 1 to 12 or carbon number 1 to 12.R 6And R 7Independent is the thiazolinyl of the straight chain of the alkyl of straight chain of carbon number 1 to 12 or carbon number 2 to 12.In order to improve ceiling temperature, in those compound, 1, the steric configuration of 4-cyclohexylidene is the trans cis that is better than.
Compound (1) is that compound (1-1-1) is to compound (1-7-1) preferably.Better compound (1) is compound (1-1-1), compound (1-3-1), compound (1-5-1) and compound (1-7-1).Good especially compound (1) is compound (1-1-1) and compound (1-5-1).Compound (2) is that compound (2-1-1), compound (2-1-2), compound (2-2-1), compound (2-3-1) are compound (2-3-5), compound (2-4-1) and compound (2-4-2) preferably.Better compound (2) is compound (2-1-2), compound (2-3-1), compound (2-3-3) and compound (2-4-1).Good especially compound (2) is compound (2-1-2) and compound (2-3-3).Compound (3) is that compound (3-1-1) is to compound (3-10-1) preferably.Better compound (3) is compound (3-1-1), compound (3-3-1), compound (3-4-1), compound (3-6-1) and compound (3-10-1).Good especially compound (3) is compound (3-1-1), compound (3-4-1) and compound (3-6-1).Compound (4) is that compound (4-1-1) is to compound (4-7-1) preferably.Better compound (4) is compound (4-1-1), compound (4-2-1), compound (4-3-1), compound (4-4-1) and compound (4-5-1).Good especially compound (4) is compound (4-1-1), compound (4-3-1) and compound (4-5-1).
Figure BPA00001328390700151
Figure BPA00001328390700171
Figure BPA00001328390700181
The 6th, explanation can be mixed to the additive in the constituent.This kind additive is optically active compound, antioxidant, UV light absorber, pigment, defoamer, polymerisable compound, polymerization initiator etc.For the spirane structure (helical structure) that brings out liquid crystal is given torsion(al)angle, and optically active compound is mixed in the constituent.The example of this kind compound is that compound (5-1) is to compound (5-4).The ratio preferably of optically active compound is smaller or equal to 5 weight percents.Better ratio is the scope of 0.01 weight percent to 2 weight percent.
Figure BPA00001328390700191
In order to prevent because of in atmosphere, heating the resistivity decreased that caused or in order not only at room temperature and at high temperature also to keep big voltage retention after using element, and antioxidant is mixed in the constituent long-time.
Figure BPA00001328390700192
The example preferably of antioxidant is that n is compound (6) of 1 to 9 integer etc.In compound (6), n is 1,3,5,7 or 9 preferably.Better n is 1 or 7.N is that 1 compound (6) is because of volatility is bigger, so effective when preventing when heating the resistivity decreased that is caused in atmosphere.N is that 7 compound (6) is less because of volatility, thus when long-time not only at room temperature and at high temperature also keep after using element aspect the big voltage retention effective.In order to obtain its effect, the ratio preferably of antioxidant is more than or equal to 50ppm, and for ceiling temperature being descended or lower limit temperature being risen, the ratio preferably of antioxidant is smaller or equal to 600ppm.Better ratio is the scope of 100ppm to 300ppm.
The example preferably of UV light absorber is benzophenone (benzophenone) derivative, benzoic ether (benzoate) derivative, triazole (triazole) derivative etc.As the photostabilizer with sterically hindered amine (amine) is also better.In order to obtain its effect, the ratio preferably of those absorption agents or stablizer is more than or equal to 50ppm, and for ceiling temperature being descended or lower limit temperature being risen, the ratio preferably of those absorption agents or stablizer is smaller or equal to 10000ppm.Better ratio is the scope of 100ppm to 10000ppm.
(guest host, the GH) element of pattern will be that pigment, anthraquinone (anthraquinone) are that the dichroism pigment (dichroic dye) of pigment etc. is mixed in the constituent as azo (azo) in order to be suitable for the host and guest.The ratio preferably of pigment is the scope of 0.01 weight percent to 10 weight percent.In order to prevent to bubble, and dimethyl silicone oil (dimethyl silicone oil), methyl phenyl silicone oil defoamers such as (methyl phenyl silicone oil) are mixed in the constituent.In order to obtain its effect, the ratio preferably of defoamer is more than or equal to 1ppm; Bad in order to prevent to show, the ratio preferably of defoamer is smaller or equal to 1000ppm.The better ratio of defoamer is the scope of 1ppm to 500ppm.
For be suitable for polymkeric substance continue orientation (polymer sustained alignment, the PSA) element of pattern, and with polymerisable compound to constituent.The example preferably of polymerisable compound is the compound that acrylate (acrylate), methacrylic ester (methacrylate), vinyl compound, vinyloxy group (vinyloxy) compound, propenyl ether (propenylether), epoxy (epoxy) compound (oxyethane (oxirane), trimethylene oxide (oxetane)), vinyl ketone (vinyl ketone) etc. have polymerizable groups.Good especially example is the derivative of acrylate or methacrylic ester.In order to obtain its effect, the ratio preferably of polymerisable compound is more than or equal to 0.05 weight percent; Bad in order to prevent to show, the ratio preferably of polymerisable compound is smaller or equal to 10 weight percents.Better ratio is the scope of 0.1 weight percent to 2 weight percent.Polymerisable compound be preferably photopolymerization initiator etc. suitably initiator in the presence of (Ultraviolet, UV) irradiation waits and polymerization by ultraviolet ray.Be used for the suitable type of polymeric felicity condition, initiator and suitable amount for haveing the knack of known to this operator, and record in the literature.For example Irgacure651 (registered trademark), Irgacure184 (registered trademark) or the Darocure1173 (registered trademark) (vapour clings to Japanese K.K. (Ciba Japan K.K.)) as the photopolymerization initiator is comparatively suitable for radical polymerization.Polymerisable compound is preferably the photopolymerization initiator in the scope that contains 0.1 weight percent to 5 weight percent.Good especially is contains photopolymerization initiator in the scope of 1 weight percent to 3 weight percent.
The 7th, the synthesis method of component cpd is described.Those compounds can synthesize by known method.Following illustration synthesis method.Compound (1-2-2) is to open the method synthetic that is disclosed in the 2000-008040 communique by the Japanese Patent spy.Compound (2-2-1) is to open the method synthetic that is disclosed in the 2005-35986 communique by the Japanese Patent spy.Compound (3-1-1) and compound (3-4-1) are the method synthetic that is disclosed by in the special fair 4-30382 communique of Japanese Patent.Compound (4-1-1) and compound (4-3-1) are the method synthetic that is disclosed by in the flat 2-503441 communique of the special table of Japanese Patent.Antioxidant is a commercially available product.The n of formula (6) is that 1 compound can be buied from Ao Er Delhi (Aldrich) company (Sigma-Aldrich Corporation).N is that compound (6) of 7 etc. is the method synthetic that is disclosed by in No. 3660505 specification sheets of United States Patent (USP).
The compound of not putting down in writing synthesis method can be by organic synthesis (Organic Syntheses, John Wiley ﹠amp; Sons, Inc), organic reaction (Organic Reactions, John Wiley ﹠amp; Sons, Inc), the method put down in writing in the organic synthesis complete works (Comprehensive Organic Synthesis, Pergamon Press), new experimental chemistry lecture books such as (ball are kind) synthesizes.Constituent is to be prepared by the compound that obtains in this way by known method.For example component cpd is mixed, by heating it is dissolved mutually then.
The purposes of constituent is described at last.Most of constituent has lower limit temperature smaller or equal to-10 ℃, more than or equal to the optical anisotropy of the scope of 70 ℃ ceiling temperatures and 0.07 to 0.20.The element that contains this constituent has big voltage retention.This constituent is suitable for the AM element.This constituent is particularly suitable for penetrating type AM element.By the ratio of control component cpd or by mixing other liquid crystal compounds, also can prepare optically anisotropic constituent with scope of 0.08 to 0.25.This constituent can be used as and has nematic constituent, and can be by adding optically active compound as the optical activity constituent.
This constituent can be used in the AM element.And then also can be used in the PM element.This constituent can be used in have PC, TN, in the AM element and PM element of STN, ECB, OCB, IPS, VA, PSA isotype.Good especially is to use in the AM element with IPS or VA pattern.Those elements can be reflection-type, penetrating type or semi penetration type.Be preferably and be used in the penetrating type element.Also can be used in non-crystalline silicon-TFT element or polysilicon-TFT element.Also can be used in this constituent is made microcapsule (microcapsule) and camber line arrangement nematic phase (the nematic curvilinear aligned phase of making, NCAP) element of type or in constituent, form the polymer dispersed that three-dimensional netted polymer forms (polymer dispersed is PD) in the element of type.
[example]
When sample is constituent, directly measure, and put down in writing the value that is obtained.When sample is compound, the preparation sample by this compound (15 weight percent) being mixed in the mother liquor crystalline substance (85 weight percent).Utilize extrapotation (extrapolation), calculate the characteristic value of compound by the value that obtains by mensuration.(extrapolated value)={ (measured value of sample)-0.85 * (measured value of mother liquor crystalline substance) }/0.15.When smectic phase (or crystallization) is separated out under this ratio, the ratio of compound and mother liquor crystalline substance is changed to 10 weight percents in regular turn: 90 weight percents, 5 weight percents: 95 weight percents, 1 weight percent: 99 weight percents under 25 ℃.Obtain the value of the ceiling temperature relevant, optical anisotropy, viscosity and dielectric constant anisotropy with compound by this extrapotation.
The composition of mother liquor crystalline substance is as described below.Each components in proportions is weight percentage.
Figure BPA00001328390700211
The mensuration of characteristic is to carry out according to following method.Those methods mostly are the method put down in writing among EIAJ's standard (Standard of Electric Industries Association of Japan) EIAJED-2521A greatly or to the method for its correct.
Nematic ceiling temperature (NI: ℃): sample is put on the hot-plate of the fusing point test device that possesses polarizing microscope, heated with the speed of 1 ℃/min.Temperature when the part of mensuration sample is changed to isotropic liquid by nematic phase.Sometimes abbreviate nematic ceiling temperature as " ceiling temperature ".
Nematic lower limit temperature (T C: ℃): will have nematic sample and put into vial, keeping was observed mesomorphic phase after 10 days in the refrigerator (freezer) of 0 ℃ ,-10 ℃ ,-20 ℃ ,-30 ℃ and-40 ℃.For example keep down nematic states at-20 ℃ at sample, when under-30 ℃, being changed to crystallization or smectic phase, with T CBe recited as≤-20 ℃.Sometimes abbreviate nematic lower limit temperature as " lower limit temperature ".
(volume vicosity: η measures down at 20 ℃ viscosity, mPas): measure and be to use E type rotational viscosimeter.
Optical anisotropy (the specific refractory power anisotropy: Δ n, measure down at 25 ℃): use the light of wavelength, utilize the Abb (Abbe refractometer) that Polarizer is installed on ocular lens to measure as 589nm.Behind the surface of a direction friction headprism, sample is dripped on headprism.When polarization direction is parallel with frictional direction, measure refractive index n ∥.When polarization direction is vertical with frictional direction, measure refractive index n ⊥.Come the anisotropic value of calculating optical according to the formula of Δ n=n ∥-n ⊥.
Dielectric constant anisotropy (Δ ε: measure down at 25 ℃): the formula according to Δ ε=ε ∥-ε ⊥ is calculated the value of dielectric constant anisotropy.Measure specific inductivity (ε ∥ and ε ⊥) as follows.
1) mensuration of specific inductivity (ε ∥): on glass substrate, be coated with (20mL) solution of octadecyltriethoxy silane (octadecyl triethoxys ilane) ethanol (ethanol) (0.16mL) through fully cleaning.After utilizing turner (spinner) to make the glass substrate rotation, heated 1 hour down at 150 ℃.The interval (cell gap) of sample being put into 2 sheet glass substrates is the VA element of 4 μ m, utilizes by UV cured caking agent this element sealing.This element is applied sine wave, and (0.5V 1kHz), measures the specific inductivity (ε ∥) on the long axis direction of liquid crystal molecule after 2 seconds.
2) mensuration of specific inductivity (ε ⊥): on glass substrate, be coated with polyimide (polyimide) solution through fully cleaning.After this glass substrate calcined, to the gained alignment film rub (rubbing) handle.The interval (cell gap) of sample being put into 2 sheet glass substrates is that 9 μ m, torsion(al)angle are the TN element of 80 degree.This element is applied sine wave, and (0.5V 1kHz), measures the specific inductivity (ε ⊥) on the short-axis direction of liquid crystal molecule after 2 seconds.
Critical voltage (Vth: measure down at 25 ℃, V): measure the LCD5100 type luminance meter that is to use big tomb electronics (OTSUKA ELECTRONICS) limited-liability company to make.Light source is halogen lamp (halogen lamp).The interval (cell gap) of sample being put into 2 sheet glass substrates is that 4 μ m, frictional direction are the normal VA element that shows black pattern (normally black mode) of antiparallel (antiparallel), utilizes UV hardened caking agent with this element sealing.The voltage (60Hz, square wave) that this element is applied is to increase to 20V from 0V interimly, increases 0.02V at every turn.At this moment, to the element irradiates light, and measure the light quantity of piercing elements from vertical direction.Make this light quantity when reaching maximum penetration coefficient be 100%, this light quantity hour penetration coefficient be voltage-penetration coefficient curve of 0%.Critical voltage is the voltage that penetration coefficient became 10% o'clock.
(VHR-1:25 ℃, %): employed TN element has the polyimide alignment film to voltage retention during mensuration, and the interval of 2 sheet glass substrates (cell gap) is 5 μ m.After sample is put into this element, utilize by ultraviolet ray and carry out the polymeric caking agent this element sealing.This TN element is applied pulsed voltage (applying 60 microseconds with 5V) and charges.Utilize the high speed potentiometer to measure the voltage of decay in during 16.7 milliseconds, obtain voltage curve in the unit period and the area A between the transverse axis.The area of area B when not decaying.Voltage retention is the per-cent of area A with respect to area B.
(VHR-2:80 ℃, %): employed TN element has the polyimide alignment film to voltage retention during mensuration, and the interval of 2 sheet glass substrates (cell gap) is 5 μ m.After sample is put into this element, utilize by ultraviolet ray and carry out the polymeric caking agent this element sealing.Apply pulsed voltage (applying 60 microseconds) and charge to this TN element with 5V.Utilize the high speed potentiometer to measure the voltage of decay in during 16.7 milliseconds, obtain voltage curve in the unit period and the area A between the transverse axis.The area of area B when not decaying.Voltage retention is the per-cent of area A with respect to area B.
Voltage retention (VHR-3:25 ℃, %): behind irradiation ultraviolet radiation, measure voltage retention, and estimate to ultraviolet stability.Constituent with big VHR-3 has big stability to ultraviolet ray.Employed TN element has the polyimide alignment film during mensuration, and cell gap is 5 μ m.Sample is injected this element, and irradiates light is 20 minutes then.Light source is extra-high-pressure mercury vapour lamp (extra high pressure mercury lamp) USH-500D (manufacturing of excellent will prosperous (USHIO) motor), element and light source be spaced apart 20cm.In the mensuration of VHR-3, measure the voltage of decay in during 16.7 milliseconds.VHR-3 is preferably more than or equal to 90%, is more preferably more than or equal to 95%.
Voltage retention (VHR-4:25 ℃, %): measure voltage retention then, and estimate the stability to heat 80 ℃ thermostatic bath internal heating 500 hours by the TN element that will be injected with sample.Constituent with big VHR-4 has big stability to heat.In the mensuration of VHR-4, measure the voltage of decay in during 16.7 milliseconds.
Time of response (τ: measure down at 25 ℃, ms): measure the LCD5100 type luminance meter that is to use big tomb electronics limited-liability company to make.Light source is a halogen lamp.Low-pass filter (Low-pass filter) is to be set at 5kHz.The interval (cell gap) of sample being put into 2 sheet glass substrates is that 4 μ m, frictional direction are the antiparallel normal VA element that shows black pattern (normally black mode), utilizes UV hardened caking agent with this element sealing.This element is applied square wave (60Hz, 10V, 0.5 second).At this moment, to the element irradiates light, and measure the light quantity of piercing elements from vertical direction.Penetration coefficient was 100% when this light quantity reached maximum, and this light quantity hour penetration coefficient is 0%.Time of response is that penetration coefficient is changed to the 10% needed time (fall time: fall time, millisecond) by 90%.
Resistivity (ρ: measure Ω cm at 25 ℃ down): the sample of 1.0mL is injected the container that possesses electrode.This container is applied volts DS (10V), measure the galvanic current after 10 seconds.Calculate resistivity according to following formula.(resistivity)={ (voltage) * (electric capacity of container) }/{ (galvanic current) * (specific inductivity of vacuum) }.
Gas chromatographic analysis: the GC-14B type gas chromatograph (gas chromatograph) that uses Shimadzu Seisakusho Ltd. to make in the mensuration.Carrier gas (carrier gas) be helium (helium) (2mL/min).Sample evaporation chamber is set at 280 ℃, and (flame ion detector (Flame Ionization Detector, FID)) is set at 300 ℃ with detector.When carrying out the separation of component cpd, (length is 30m to capillary column (capillary column) DB-1 that uses Agilent Technologies (Agilent Technologies Inc.) to make, and internal diameter is 0.32mm, and thickness is 0.25 μ m; Fixed liquid phase is dimethyl polysiloxane (dimethylpolysiloxane); Nonpolarity).With this tubing string 200 ℃ down keep 2 minutes after, be warming up to 280 ℃ with the speed of 5 ℃/min.Specimen preparation is become acetone (acetone) solution (0.1 weight percent), and wherein 1 μ L is injected in the sample evaporation chamber.C-R5A type Chromatopac or its equal product that Shimadzu Seisakusho Ltd. makes counted in record.The gas chromatography figure that is obtained (gas chromatogram) expression and the residence time (retention time) of the corresponding crest of component cpd (peak) and the area of crest.
Solvent in order to the dilution sample also can use chloroform (chloroform), hexane (hexane) etc.For component cpd is separated, also can use following capillary column: (length is 30 ° of m to the HP-1 that Agilent Technologies Inc. makes, internal diameter is 0.32mm, thickness is 0.25 μ m), (length is 30m to the Rtx-1 that makes of Leix Imtech (Restek Corporation), internal diameter is 0.32mm, thickness is 0.25 μ m), (length is 30m to the BP-1 that makes of SGE international corporation (SGE International Pty.Ltd), internal diameter is 0.32mm, and thickness is 0.25 μ m).In order to prevent the overlapping of compound crest, the capillary column CBP1-M50-025 (length is 50m, and internal diameter is 0.25mm, and thickness is 0.25 μ m) that also can use Shimadzu Seisakusho Ltd. to make.
The ratio of the liquid crystal compounds that is contained in the constituent can be calculated by following method.Liquid crystal compounds can utilize gas chromatograph to detect.The area of the crest among the gas chromatography figure is than the ratio that is equivalent to liquid crystal compounds (mole number).In the use the literary composition put down in writing capillary column the time, also the correction factor (correction factor) of each liquid crystal compounds can be considered as 1.Therefore, the ratio of liquid crystal compounds (weight percent) is recently to calculate according to the area of crest.
Describe the present invention in detail by example.The present invention is not subjected to the qualification of following example.Compound in comparative example and the example is based on the definition of following table 3 and utilizes symbol to represent.
In table 3, with 1, the relevant steric configuration of 4-cyclohexylidene is trans.Numbering in the bracket of example meta behind symbol is corresponding to the numbering of compound.The symbol of (-) is meant other liquid crystal compounds.The ratio of liquid crystal compounds (per-cent) is the weight percent (wt%) of described additive with respect to the gross weight of liquid-crystal composition, contains impurity in the liquid-crystal composition in addition.At last, the characteristic value that gathers constituent.
Table 3 uses the representation of the compound of symbol
R-(A 1)-Z 1-……-Z n-(A n)-R’
Figure BPA00001328390700251
[comparative example 1]
Open selection example 19 in the constituent that is disclosed in the 2001-262145 communique from the Japanese Patent spy.It is according to being that this constituent contains compound (1-5-1), compound (3-1-1), compound (3-2-1) and compound (3-4-1), and the viscosity minimum.The composition and the characteristic of this constituent are as described below.
Figure BPA00001328390700261
NI＝80.4℃；Tc≤-20℃；Δn＝0.077；η＝14.3mPa·s；Δε＝-1.4.
[comparative example 2]
Open selection example 12 in the constituent that is disclosed in the 2001-115161 communique from the Japanese Patent spy.It is according to being that this constituent contains compound (1-1-1), compound (1-2-1), compound (1-5-1), compound (3-1-1), compound (3-2-1) and compound (3-4-1), and the η minimum.The composition and the characteristic of this constituent are as described below.
Figure BPA00001328390700262
NI＝72.0℃；Tc≤-20℃；Δn＝0.076；η＝16.2mPa·s；Δε＝-1.2.
[example 1]
Figure BPA00001328390700263
NI＝81.8℃；Tc≤-20℃；Δn＝0.089；η＝13.3mPa·s；Δε＝-3.0；Vth＝2.38V；VHR-1＝99.2％；VHR-2＝98.2％；VHR-3＝98.1％.
[example 2]
Figure BPA00001328390700272
NI＝70.5℃；Tc≤-20℃；Δn＝0.090；η＝11.9mPa·s；Δε＝-2.7；VHR-1＝99.1％；VHR-2＝98.1％；VHR-3＝98.0％.
[example 3]
Figure BPA00001328390700273
NI＝73.9℃；Tc≤-20℃；Δn＝0.100；η＝12.7mPa·s；Δε＝-2.6；VHR-1＝99.1％；VHR-2＝98.1％；VHR-3＝98.1％.
[example 4]
Figure BPA00001328390700281
NI＝70.6℃；Tc≤-20℃；Δn＝0.083；η＝13.2mPa·s；Δε＝-2.9；VHR-1＝99.0％；VHR-2＝98.1％；VHR-3＝98.0％.
[example 5]
Figure BPA00001328390700282
NI＝84.1℃；Tc≤-20℃；Δn＝0.090；η＝12.8mPa·s；Δε＝-2.4；VHR-1＝99.2％；VHR-2＝98.2％；VHR-3＝98.1％.
[example 6]
Figure BPA00001328390700291
NI＝96.6℃；Tc≤-20℃；Δn＝0.090；η＝11.6mPa·s；Δε＝-2.3；VHR-1＝99.2％；VHR-2＝98.2％；VHR-3＝98.2％.
[example 7]
Figure BPA00001328390700292
NI＝72.5℃；Tc≤-20℃；Δn＝0.087；η＝13.2mPa·s；Δε＝-2.1；VHR-1＝99.1％；VHR-2＝98.1％；VHR-3＝98.0％.
[example 8]
Figure BPA00001328390700293
NI＝80.8℃；Tc≤-20℃；Δn＝0.086；η＝12.6mPa·s；Δε＝-2.6；VHR-1＝99.0％；VHR-2＝98.1％；VHR-3＝98.0％.
[example 9]
Figure BPA00001328390700294
NI＝73.5℃；Tc≤-20℃；Δn＝0.088；η＝13.0mPa·s；Δε＝-2.7；VHR-1＝99.1％；VHR-2＝98.2％；VHR-3＝98.0％.
[example 10]
Figure BPA00001328390700302
NI＝71.9℃；Tc≤-20℃；Δn＝0.084；η＝13.0mPa·s；Δε＝-2.6；VHR-1＝99.1％；VHR-2＝98.1％；VHR-3＝98.1％.
[example 11]
Figure BPA00001328390700303
NI＝72.7℃；Tc≤-20℃；Δn＝0.081；η＝12.9mPa·s；Δε＝-2.7；VHR-1＝99.1％；VHR-2＝98.1％；VHR-3＝98.0％.
Figure BPA00001328390700311
NI＝71.6℃；Tc≤-20℃；Δn＝0.072；η＝12.5mPa·s；Δε＝-3.0；VHR-1＝99.0％；VHR-2＝98.0％；VHR-3＝98.0％.
[example 13]
NI＝75.0℃；Tc≤-20℃；Δn＝0.072；η＝12.7mPa·s；Δε＝-2.7；VHR-1＝99.2％；VHR-2＝98.2％；VHR-3＝98.1％.
[example 14]
Figure BPA00001328390700313
Figure BPA00001328390700321
NI＝74.1℃；Tc≤-20℃；Δn＝0.091；η＝12.7mPa·s；Δε＝-2.6；VHR-1＝99.3％；VHR-2＝98.1％；VHR-3＝98.0％.
[example 15]
NI＝72.3℃；Tc≤-20℃；Δn＝0.083；η＝12.4mPa·s；Δε＝-3.1；VHR-1＝99.1％；VHR-2＝98.0％；VHR-3＝98.0％.
[example 16]
Figure BPA00001328390700323
Figure BPA00001328390700331
NI＝74.5℃；Tc≤-20℃；Δn＝0.084；η＝12.7mPa·s；Δε＝-3.1；VHR-1＝99.2％；VHR-2＝98.1％；VHR-3＝98.0％.
[example 17]
NI＝72.7℃；Tc≤-20℃；Δn＝0.076；η＝12.8mPa·s；Δε＝-2.6；VHR-1＝99.3％；VHR-2＝98.2％；VHR-3＝98.1％.
[example 18]
Figure BPA00001328390700333
Figure BPA00001328390700341
NI＝78.4℃；Tc≤-20℃；Δn＝0.089；η＝12.8mPa·s；Δε＝-2.7；VHR-1＝99.3％；VHR-2＝98.2％；VHR-3＝98.2％.
[example 19]
Figure BPA00001328390700342
NI＝74.8℃；Tc≤-20℃；Δn＝0.085；η＝12.9mPa·s；Δε＝-2.7；VHR-1＝99.1％；VHR-2＝98.1％；VHR-3＝98.1％.
The constituent of example 1 to 19 is compared with the constituent of comparative example 1 and comparative example 2, has big negative dielectric constant anisotropy and little viscosity.Thus, liquid-crystal composition of the present invention has than the more excellent characteristic of liquid-crystal composition that is disclosed in patent documentation 1 and 2.
Liquid-crystal composition of the present invention at nematic ceiling temperature height, nematic lower limit temperature is low, viscosity is little, optical anisotropy is suitable, negative dielectric constant anisotropy is big, resistivity big, in, the stable high characteristic to heat high to ultraviolet stability, fully possess at least a characteristic or have suitable balance at least two specific characters.Since the liquid crystal display device that contains this kind constituent become have the short time of response, the AM element of big voltage retention, big contrast gradient, long lifetime etc., therefore can be used for liquid crystal projector, LCD TV etc.

Claims (25)

1. liquid-crystal composition, it is characterized in that it contains being selected from at least a compound in the group of the represented compound of formula (1) and being selected from at least a compound in the group of the represented compound of formula (2) as second composition as first composition, and described liquid-crystal composition has negative dielectric constant anisotropy
Figure FPA00001328390600011
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring A independently is a tetrahydropyrans-2,5-two bases, 1,4-cyclohexylidene or 1, the 4-phenylene, and at least one to encircle A be tetrahydropyrans-2,5-two bases; Ring B and ring C independently are 1,4-cyclohexylidene or 1,4-phenylene; Z 1And Z 2Independent is singly-bound, ethylidene, inferior methoxyl group or carbonyl oxygen base; M is 1,2 or 3; P and q independently are 0,1,2 or 3, and p and q's and smaller or equal to 3.
2. liquid-crystal composition according to claim 1 is characterized in that first composition wherein is to be selected from at least a compound of formula (1-1) to the group of the represented compound of formula (1-7),
Figure FPA00001328390600021
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12.
3. liquid-crystal composition according to claim 2 is characterized in that first composition wherein is to be selected from at least a compound of formula (1-1) to the group of the represented compound of formula (1-3).
4. liquid-crystal composition according to claim 2 is characterized in that first composition is to be selected from at least a compound of formula (1-4) to the group of the represented compound of formula (1-7).
5. liquid-crystal composition according to claim 2, it is characterized in that, wherein first composition be selected from formula (1-1) to the group of the represented compound of formula (1-3) at least a compound and with the mixture of at least a compound of formula (1-4) to the group of the represented compound of formula (1-7).
6. according to the described liquid-crystal composition of arbitrary claim in the claim 1 to 5, it is characterized in that second composition wherein is to be selected from at least a compound of formula (2-1) to the group of the represented compound of formula (2-4),
Figure FPA00001328390600031
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring B 1, the ring B 2, the ring C 1, and the ring C 2Independently be 1,4-cyclohexylidene or 1,4-phenylene; Z 1And Z 2Independent is singly-bound, ethylidene, inferior methoxyl group or carbonyl oxygen base; Z 4Be ethylidene, inferior methoxyl group or carbonyl oxygen base.
7. liquid-crystal composition according to claim 6 is characterized in that wherein second composition is at least a compound that is selected from in the group of the represented compound of formula (2-3).
8. liquid-crystal composition according to claim 6 is characterized in that wherein second composition is at least a compound that is selected from in the group of the represented compound of formula (2-4).
9. according to the described liquid-crystal composition of arbitrary claim in the claim 1 to 8, it is characterized in that wherein gross weight with respect to liquid-crystal composition, first components in proportions is the scope of 5 weight percent to 70 weight percents, and second components in proportions is the scope of 5 weight percent to 30 weight percents.
10. according to the described liquid-crystal composition of arbitrary claim in the claim 1 to 9, it is characterized in that it contains as ternary being selected from at least a compound in the group of the represented compound of formula (3),
Herein, R 3And R 4The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring D and ring E independently are 1,4-cyclohexylidene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,5-two fluoro-1,4-phenylene; Z 3Independent is singly-bound, ethylidene or carbonyl oxygen base; J is 1,2 or 3.
11. liquid-crystal composition according to claim 10 is characterized in that the 3rd composition wherein is to be selected from at least a compound of formula (3-1) to the group of the represented compound of formula (3-10),
Figure FPA00001328390600041
Herein, R 3And R 4The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12.
12. liquid-crystal composition according to claim 11 is characterized in that wherein the 3rd composition is at least a compound that is selected from in the group of the represented compound of formula (3-1).
13. liquid-crystal composition according to claim 11 is characterized in that the 3rd composition wherein is to be selected from at least a compound in the group of the represented compound of formula (3-1) and with the mixture of at least a compound in the group of the represented compound of formula (3-4).
14. liquid-crystal composition according to claim 11 is characterized in that the 3rd composition wherein is to be selected from at least a compound in the group of the represented compound of formula (3-1) and with the mixture of at least a compound in the group of the represented compound of formula (3-6).
15. liquid-crystal composition according to claim 11 is characterized in that the 3rd composition wherein is to be selected from at least a compound in the group of the represented compound of formula (3-6) and with the mixture of at least a compound in the group of the represented compound of formula (3-10).
16. liquid-crystal composition according to claim 11 is characterized in that the 3rd composition wherein is to be selected from at least a compound in the group of the represented compound of formula (3-1), with at least a compound in the group of the represented compound of formula (3-4) and with the mixture of at least a compound in the group of the represented compound of formula (3-6).
17., it is characterized in that wherein with respect to the gross weight of liquid-crystal composition, ternary ratio is the scope of 30 weight percent to 70 weight percents according to the described liquid-crystal composition of arbitrary claim in the claim 10 to 16.
18. according to the described liquid-crystal composition of arbitrary claim in the claim 1 to 17, it is characterized in that it more contains as being selected from at least a compound in the group of the represented compound of formula (4) of four-component,
Figure FPA00001328390600051
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12; Ring F independently is 1,4-cyclohexylidene or 1,4-phenylene; Z 3Independent is singly-bound, ethylidene or carbonyl oxygen base; X 1And X 2Independent is fluorine or chlorine; K is 1,2 or 3.
19. liquid-crystal composition according to claim 18 is characterized in that four-component wherein for being selected from at least a compound of formula (4-1) to the group of the represented compound of formula (4-7),
Figure FPA00001328390600061
Herein, R 1And R 2The thiazolinyl of independent alkoxyl group, carbon number 2 to 12 or the thiazolinyl of the carbon number 2 to 12 that replaced by fluorine of hydrogen arbitrarily for the alkyl of carbon number 1 to 12, carbon number 1 to 12.
20. liquid-crystal composition according to claim 19 is characterized in that wherein four-component is for to be selected from at least a compound in the group of the represented compound of formula (4-1).
21. liquid-crystal composition according to claim 19 is characterized in that four-component wherein is for being selected from at least a compound in the group of the represented compound of formula (4-1) and with the mixture of at least a compound in the group of the represented compound of formula (4-5).
22., it is characterized in that wherein with respect to the gross weight of liquid-crystal composition, the ratio of four-component is the scope of 5 weight percent to 55 weight percents according to the described liquid-crystal composition of arbitrary claim in the claim 18 to 21.
23. according to the described liquid-crystal composition of arbitrary claim in the claim 1 to 22, it is characterized in that wherein nematic ceiling temperature is more than or equal to 70 ℃, optical anisotropy under 25 ℃, wavelength 589nm is more than or equal to 0.08, and at 25 ℃, dielectric constant anisotropy when frequency is 1kHz smaller or equal to-2.
24. a liquid crystal display device is characterized in that it contains just like the described liquid-crystal composition of arbitrary claim in the claim 1 to 23.
25. liquid crystal display device according to claim 24, wherein the operating mode of liquid crystal display device is that vertical alignment mode, transverse electric field switch mode or polymkeric substance continue alignment mode, and the type of drive of liquid crystal display device is the active-matrix mode.
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